Modified aminoplast resins



Patented Sept. 7, 1954 UNITED STATES PATENT OFFICE MODIFIED AMINOPLAST RESINS Tzeng J iueq Suen, Stamford, Conn., assignor to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application June 11, 1952, Serial No. 292,992

8 Claims.

This invention relates to novel molding compositions comprising urea-formaldehyde resins or melamine-formaldehyde resins modified with a substituted propane having the general formula:

dehyde resins modified by addition thereto of a substituted propane, such as those having the general formula:

wherein R is a member selected from the group consisting of methyl and ethyl, and n and n are integers between 2-6 inclusive, and m and m are integers between l-6 inclusive.

A further object of the present invention is to produce molding compositions having diminished tendency to display both mold shrinkage and after shrinkage in a molded article. A further object of the present invention is to use the reaction products as defined hereinabove as flow promoters for resinous compositions, such as urea-formaldehyde resins, melamine-formaldehyde'resins and the like. These and other objects of the present invention will be discussed more completely hereinbelow.

The substituted propanes used in the composition of the present invention may be prepared in a number of different ways. (1) one may, for instance, prepare these novel substituted propanes by reacting under alkaline conditions (a) a compound having the general formula .l-halo, 2-hydroxy, 3-alkoxyalkyleneoxy-propane, wherein said alkoxy group contains between 1-2 carbon atoms inclusive and said alkyleneoxy group is derived from adiprimary straight chain aliphatic alcohol containing 1-6 alkyleneoxy groups, in which each alkyleneoxy group contains 2-6 carbon atoms, with (b) a diprimary saturated aliphatic straight chain alcoholcontaining 1-6 a1- kyleneoxy groups in which each alkyleneoxy group contains 2-6 carbon atoms. (2) A further method of preparation which may be used in producing these compounds comprises reacting (a) a compound of the general description 1,2- epoxy, 3-alkoxyalkyleneoxy-propane, wherein the alkoxy group contains 1-2 carbon atoms inclusive, and wherein said alkyleneoxy group is derived from a diprimary aliphatic straight chain alcohol containing 1-6 alkyleneoxy groups and in which each alkyleneoxy group contains 2-6 carbon atoms inclusive, with (.b) a diprimary aliphatic straight chain alcohol containing 1-6 alkyleneoxy groups, in which each alkyleneoxy group contains 2-6 carbon atoms. This latter reaction can be accomplished under either acid or alkaline conditions. However, acid conditions are preferred. (3) A still further modification of the process of preparing the novel compounds of the present invention can be accomplished by reacting (a) a compound having the general formula l-halo, Z-hydroxy, 3-hydroXyalky1eneoxy-propane, wherein the halo group may be any one of the halogens, such as chlorine, bromine, iodine,

or fluorine, and wherein the alkyleneoxy group is derived from a diprimary straight chained aliphatic alcohol containing 1-6 alkyleneoxy'groups in which each alkyleneoxy group contains '2-6 carbon atoms, with (b) a mono-alkyl ether of a diprimary aliphatic straight chained alcohol, wherein. the alkylgroup is a member of the group consisting of methyl and ethyl, and wherein the iprimary straight chained aliphatic alcohol contains between 1 and 6 alkyleneoxy groups, and in which each alkyleneoxy group contains 2-6 carbon atoms. This latter reaction must be performed under alkaline conditions. (4) Astill further method of preparing the novel compounds of the present invention can be accomplished by reacting (a) acompound of the general description: 1,2-epoxy, 3-hydroxyalkyleneoxy-propane, with (b) a monoalkyl ether of a diprimary aliphatic straight chained alcohol, wherein said alkyleneoxy group is derived from a diprimary aliphatic straight chained alcohol containing l-6 alkyleneoxygroups, in which each alkyleneoxy group contains 2-6 carbon atoms, and wherein said alkyl group is a member of the group methyl and ethyl, and wherein said diprimary straight chained aliphatic alcohol contains 1-6 alkyleneoxy groups in which each alkyleneoxy group contains 2-6 carbon atoms. This latter reaction can be acomplished under either acid or alkaline conditions. However, acid condition is preferred.

In the above general processes, the reactions under either alkaline or acid conditions, when using the epoxy compounds, do not require molar quantities of acid or alkali as the acid or alkali used does not enter into the reaction but rather acts as a catalyst. However, in the reactions with halo-substituted propanes performed under alkaline conditions, it is necessary for optimum results to use equimolar proportions of alkaline material and the halo-substituted propanes as the alkaline material does enter into the reaction and forms a salt with the halide radical which breaks off of the propane to form the epoxy linkage on the propane chain.

In the preparation of the substituted propanes used in the present invention, one may use either a diprimary aliphatic straight chained alcohol, such as in the general discussion of the alternative methods of preparing the compounds of the present invention as set forth above numbered 1 and 2, or the mono-methyl ethers or monoethyl ethers of the diprimary aliphatic straight chained alcohols, as set forth in the general discussion of alternative methods of preparation numbered 3 and 4. These diprimary aliphatic straight chained alcohols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, propanediol-LS; di(propanediol-l,3) structurally represented as H[O(CH2)3]2OI-I; tri(propanediol- 1,3), H[O(CH2)3]aOH; tetra(propanediol-1,3), H[O(CH2) 31401-1; penta(propanediol-1,3)

hexa(propanediol-1,3), H[O(CH2) 3] 60H; butanediol-1,4, or HO(CH2)4OH; di(butanediol-1,4) or H[O(CHz) 4]2OH; tri(butanediol-1,4) or tetra(butanediol-1,4) or H[O(CH2)4]4OH; penta- (butanediol-IA) or HEOK'CI-IzMlsOI-I; hexa(butanediol-1,4) or H[O(CH2)4]6OH; petanediol-1,5 or HO(CH2)5OH; di(pentanediol-1,5) or tri(pentanediol-1,5) or I-I[O(CHz')slsOI-I; tetra- (pentanediol-1,5) or I-I[O(CHz)5]tOH; penta- (pentanediol-1,5) or H[O(CH2) 51501-1; hexa(pentanediol-1,5') or I-I[O(CH2)5]sOI-I; hexanediol-1,6 or HO(CH2)sOH; di(hexanediol-1,6) or H[O(CI-Iz)6]2OH; tri(hex anediol-1,6) or H[O (CH2) 61301-1 tetra(hexanediol-1,6) or H[O(CH2)6]4OH; penta- (hexanediol-LG) or H[O(CH2)s]5O I-I; and hexa- (hexanediol-1,6) or H[O(CI-Iz) sleOI-I.

It has been indicated, hereinabove, (1) that the substituted propanes used in the composition of the present invention may be prepared by reacting under alkaline conditions, a compound of the general description l-halo-2-hydroxy, 3-alkoxyalkyleneoxy-propan with a diprimary straight chained aliphatic alcohol as defined hereinabove. The former of the starting materials are substituted propanes and have been described fully as to compounds per se and as to the method of preparation in my copending application, Serial No. 151,032, filed March 21, 1950, now abandoned. These substituted propanes, namely the l-halo, Z-hydroxy, 3-alkoxyalkyleneoxy-propanes may be prepared by the reaction of an epihalohydrin with a monomethyl or mono-ethyl ether of a diprimary aliphatic straight chained alcohol. The epihalohydrins may be either epichlorohydrin, epibromohydrin, epiioclohydrin or epifiuorohydrin. The compounds l-halo, Z-hydroxy, 3-alkoxyalkyleneoxy-propane, which may be used in the preparation of the compounds of the present invention, include the following, in which the radical halo includes chloro, bromo, iodo and fiuoro: l-chloro, 2-hydroxy, 3-methoxyethoxy-propane; l-bromo, 2-hydroxy, 3-ethoxyethoxy-propane; 1- iodo, Z-hydroxy, 3-methoxyethoxy-propane; 1- fiuoro, Z-hydroxy, 3-ethoxyethoxy-propane; and their halo-substituted counterparts such as 1- halo, 2-hydroxy, 3-methoxyethoxyethoxy-propane; l-halo, 2-hydroxy, 3-ethoxyethoxyethoxypropane; l-halo, 2-hydroxy, 3-methoxyethoxyethoxyethoxy-propane; l-halo, 2-hydroxy, 3- ethoxyethoxyethoxyethoxy-propane; l-halo, 2- hydroxy, 3-ethoxypropoxypropoxypropoxypropoxypropoxy propane; 1 halo, 2 hydroxy, 3 methoxypropoxypropoxypropoxypropoxypropoxypropoxy propane; 1 halo, 2 hydroxy, 3 ethoxypropoxypropoxypropoxypropoxypropoxypropoxy propane; 1 halo, 2 hydroxy, 3 methoxyhexoxyhexoxyhexoxyhexoxyhexoxyhexoxy-propane; l-halo, Z-hydroxy, 3-ethoxyhexoxyhexoxyhexoxyhexoxyhexoxyhexoxy propane.

If one chooses to prepare the compounds used in the composition of the present invention by the general process set forth under (2) hereinabove, one would react a diprimary aliphatic straight chained alcohol, as defined hereinabove, with a compound having the general formula, 1,2- epoxy, 3-alkoxyalkyleneoxy-propane, and these compounds are novel compounds and are disclosed in my copending application bearing the Serial No. 151,035, filed March 21, 1950 now abandoned. Included in the group of the 1,2- epoxy, 3-alkoxyalkyleneoxy-propane are the following compounds: 1,2-epoxy, 3-methoxyethoxypropane; 1,2-epoxy, 3-ethoxyethoxy-propane; 1,2-epoxy, 3-methoxyethoxyethoxy-propane; 1,2- epoxy, 3 ethoxyethoxyethoxy propane; 1,2 epoxy, 3-ethoxypropoxypropoxypropoxypropoxypropoxypropoxy-propane; 1,2-epoxy, 3-methoxybutoxy-propane; 1,2-epoxy, 3-ethoxybutoxy-propane; 1,2-epoxy, 3-ethoxybutoxybutoxy-propane; 1,2 epoxy, 3 methoxyhexoxyhexoxyhexoxyhexoxyhexoxyhexoxy-propane; 1,2-epoxy, B-ethoxyhexoxyhexoxyhexoxyhexoxyhexoxyhexoxy propane.

If one should choose to prepare the substituted propanes used in the present invention by reacting, under alkaline conditions, the monomethyl or the mono-ethyl ether of a diprimary aliphatic straight chained alcohol, as defined hereinabove, with a compound having the general formula l-halo, 2-hydroxy, 3-hydroxyalkyleneoxy-propane, in accordance with the general process set forth hereinabove under the identification (3), one may select as the substituted propane as a starting material any of the following: l-chloro, 2-hydroxy, 3-hydroxyethoxypropane; l-bromo, 2-hydroxy, 3-hydroxyethoxyethoxy-propane; l-iodo, 2-hydroxy, B-hydroxyethoxyethoxyethoxy propane; 1 fluoro, 2 hy droxy, 3 hydroxyethoxyethoxyethoxyethoxyethoxy-propane; or their halo-substituted counterparts in which the halo group may be chloro, bromo, iodo or fluoro, such as 1-halo, Z-hydroxy, 3 hydroxyethoxyethoxycthoxyethoxyethoxyethoxy-propane; 1 halo, 2 hydroxy, 3 hydroxypropoxy-propane; l-halo, Z-hydroxy, 3-hydroxypropoxypropoxy propane; 1 halo, 2 hydroxy, 3 hydroxypentoxypentoxypentoxypentoxypentoxypentoxy-propane; l-halo, 2-hydroxy, 3-hydroxyhexoxy-propane; and the like.

If one wishes to prepare the substituted propanes used; in the composition; of: the present invention by the. process; set: forth; hereinaboveE and identifiedas number (4%, one; neect only: react the. mono-methyl; or the: monoethyl: her" of: a; diprima-ry. aliphatic: straight chained. alcoholas, defined hereinagbove; with a. compound, having thegenera-lformulaz- LZ-epoXy; ii-hydroxyalkyleneoxy-propane; Included amongst these? latter compounds. are the,- species' 1,2-. epoxy;

3-hydroxx-ethoxyrpropaneg; L z-epoxy, 31-hy-' droxyethoxyethoxy-propane; 1,2-epoxt3. 3.-hydroxyethoxyethoxy-propa nc; 1,-2-epoxy, B-hydroxyethoxyethoxyethoxyapropaneg 1,2-epoxy; 3,- hydroxyethoxyethoxyethoxyethoxy-propane; 1,2.- epoxy; 3hydroxyethoxyethoxyethoxyethoxyetheoxyt-propane; 1,2.- epoxy 3-hydroxyethoxyetlroxyethoxyethoxyethoxyethoxyepropaneg 1,2.-epoxy, 3-hydroxypropoxy-propane; 1,2-epoxy, 3 hydroxyhexoxyhexoxyhexoxyhexoxyhexoxy propane; 1,2-epoxy, 3-hydroxyhexoxyhexoxyhexxtf exoxyhexoxyhexoicy-propane.

In order to illustrate the; methods of prepare. tionof, these substituted. propanes: generally, the following: examples are setforth. for the-purpose oil illustration only, butit must, be remembered that any and all. limitations contained-:inthese:- examplesare, not to, be interpreted as limitations onthe case, except as indicated in the appended claims. All parts. are, partsby weight- EXAMPLE." 1

Preparation of Z-h' dmry, l-hydroccyethoxy, 3.-ethoryetltomy,-propanet 548 parts of l chloro, 2-hydroxy-3-ethoxyeth-- oxy propane- (3 mole): and 7'45 par-ts of ethylene glycol (12 mole) are mixed together in a suitable reaction chamber and heatedto 80 C; A 50% solution, containing 120 parts of sodium hydrox ide: (3' mols). in water is slowly introduced with stirring: in about a twenty-minute period, while thereaction temperature is maintained at 79 8l C. Thereupon, the reaction is allowed to proceed to completion in. about atwo-hour period at the same-temperature range. Any residual alkali is: neutralized with concentrated: sulturic: acid. The product, with. the salts. filtered off; is fractionatedundervacuum with a suitable I fractionati'ng column. After removing water and excess ethylene glycol, the. 2z-hydroxy-i hydroxyethoxy-methoxyethoxy-propane is. collected: at 1'40--14A" undenabsolutepressure of 1-115 of mercury. The; total. yield: isabout izo: parts. on about 67 Qf; theoretical yield. C=51.59%; H=9.5'7%. C;=5-1.94 H=9;62%.

439 parts of 1,2-epoXys;3ethoxyethoxy=propane (3-..mols), and. 558 parts; of ethylene. glycol. (9 mols) are mixed; together in av suitable reaction chamber. parts; ofconcentrated", sulfuric acid is very slowly added: with: vigorous stirring, and: cooling. The mixture-is; then heated up; to; and maintained. at, 9G-1Q0f* for about an eight-hour: period; Theaeidis then neutralized with barium. carbonate and. the .nnxture' is; thenvfiitered. The filtrate is fractionated under vacuum with a suitable column. A ften'removingthe excess of ethylene glycol, the glyceryl-a-hydroxyethyl-a-ethoxyethylether, or 2-hydroxy, l-hydroxyethoxy, 3- ethoxyethoxy-propane, is collected at 140-144 C., under an absolute pressure of 1-1.5 mm. of mercury.

In Examples 1 and 2 it is desirable to use an excess of a diprimary aliphatic straight chained Calculated for: Gil- 2004,

Analysis: round that.

: vigorousstirringi and cooling;

6; alcohol. H-LOIYCIBY to. completeitherreactiom In. general, the usezodZy-l zmolsmf the 'dipnimary: alie phatic straight: chained alcohol: per;- mol. on the halo; or; epoxy 'compoundnis desired for; practical purposes; The temperature of therreaction isnot particularly; critical; for instance. temperatures between 70.-'1;0 05-C. would be adesirablerange;

Thelproducts used in; the present-invention are essentially.unsymmetrical; glycerol di-ethers; In the aboye. two processes, namely; in, Examples-1;. and 2, the end witlrthe. hydroxy group is first linked up before the endwitlr the alkoxy group fittedintowthei structure." Qbviously,.the sequence'could Ice-reversed. The: iollowingstwo. ex-.- amples: are. set forth for. the. purpose; ofillustratr ling-this point.

30.9w parts of l-chlor gz-hydroxy, 3.- (finhydlqxy ethoxyl-propanev 2;, mole-1., and 54(Lpartstethyleneiglycol mono-ethyl. ether (dmols) areimixed:

g (Z-hydroxtr. l-hydroxyethoxya 3-ethoxyethoxrpropane) is. collected at. 14414-1445 6., under-v an. absolute. pressure oil-l5: mm. of mercury.

236-3 parts of 1 ,2-epoxy; S-hydroxyethoxywro i pane. (2"mols); aml'x541) parts: ot'ethyleneglycol monoeethyl: ether '(fizmolsr "are mixeditogether in asuitable reaction chamber. lzzparts of'concen trated sulfuric acidaisaddedtvery slowly; with: The mixture is then heatedup. to, and maintained at, about: 80. 6. forabout.a terr-hour'period. Theacid?v isr'then. neutrali'zedcwith; barium. carbonate; and the saltthua formed is filtered off; Thefiltrate is; then'fractionated under vacuum with asuitrable fractionating column. After the excess ethylene glycoD'mono-ethyl ether has been removed-with the water, the l-hydroxyethoxy, 2- hydroxy, 3-ethoxyethoxy-propane is collected at 1 -14 C. under an absolute pressure of 1-1.5

mm. of mercury.

The compounds:- used in the presentinvention include the following: l-hydroxyethoxy, 2-hydroxy, 3 methoxyethoxy propane; l-hydroxyethcxy; 2;-hyd '1 o y, 3"-ethoxyethoxy-prop ane; 1; hydroxyethoxy; 2- hydroxy, 3.:- methoxyethoxyethoxy propane'; I-hydrQXYethOXY; 2j-hydroxy, 3; methoxyethoxyethoxy propaneyl hydroxyetm. oxy; zi-hydroxy; 3=ethoxyethoxyethoxyrpropane;

Q iZ hQ mn n I-hY YBtIi L. :11adr r. mc hoxync tq ypen oxyn n oxr pro.-. pane; l-hydroxyethoxy, Z-hydrQxy. 3-'el;hoxy;- pentoxypentoxypentoxypropane; l -hydroxyeth oxy, Z-hydroxy, 3-methoxypentoxypentoxy-pentoxypentoxy propane; 1 hydroxyethoxy, 2 hydroxy, 3-ethoxypentoxypentoxypentoxypentoxypropane; l-hydroxyethoxy, Z-hydroxy, 3-methoxypentoxypentoxypentoxypentoxypentoxy propane; 1-hydroxyhexoxyhexoxyhexoxyhexoxyhexoxyhexoxy, 2-hydroxy, 3-methoxyhexoxyhexoxyhexoxyhexoxyhexoxyhexoxy-propane.

I have discovered that when I use these modifiers for synthetic resinous molding compositions, such as the urea-formaldehyde or melamineformaldehyde molding powders, particularly do I experience the reduction in the amount of shrinkage of the articles molded with these molding powders. The following example is set forth to illustrate how this may be accomplished.

EXAMPLE 5 A urea-formaldehyde resin syrup is prepared in the conventional way with a mol ratio of formaldehyde to urea of 1.33:1, in which the reaction between the formaldehyde and urea is carried out at a pH of about 99.5 and at a temperature of about 25 C. until the free formaldehyde content drops to about 5%. Z-hydroxy, l hydroxyethoxy, 3 ethoxyethoxy propane is added as a modifier. The modified resin syrup is then mixed with alpha-cellulose pulp and the mixture is dried and then ground with a suitable curing agent and lubricant to a fine powder. The proportion of resin solidszmodifierzalphacellulose pulp is 62:5:33. In the evaluation of the molding powders prepared as described above, a molded article shows its mold shrinkage to be 4.0 mils per inch and its after shrinkage 3.9 mils per inch. An unmodified molding powder prepared in the same manner with the resin solids to alpha-cellulose ratio of 67:33 shows a mold shrinkage of 5.5 mils per inch and an after shrinkage of 8.6 mils per inch.

The determination of the shrinkage of a molded article is accomplished in the followingmanner. The shrinkage of the molded article is evaluated by means of a test piece in the form of a circular disc A" thick and. 4" in diameter and is measured in terms of mold shrinkage and after shrinkage. If the diameter of the cold mold cavity is denoted as A; the diameter of the molded disc after being conditioned at 25 C. and at a relative humidity of 50% for 48 hours is denoted as B; and the diameter of the disc after further conditioning for 48 hours at 220 F. and thereafter being cooled to 25 C. at a relative humidity of 50% is denoted as C; the following equations can be set up, in which the shrinkages are measured in terms of mils/inch.

A-C A Mold shrinkage= X 1000 After shrinkage= X 1000 Total shrinkage: X 1000 The substituted propanes of the present invention may be incorporated into the resinous material in amounts varying between about 2% and 15% by weight, based on the total weight of resin and modifier. Preferably, one could use between about 5% and 10% by weight, based on the total weight of the resin and the modifier.

This application is a continuation-in-part of my earlier application, having the Serial No. 151,033, filed March 21, 1950, now abandoned.

I claim:

1. A molding composition comprising an aminoplast resin selected from the group consisting of a melamine-formaldehyde resin and a urea" formaldehyde resin and between about 2% and 15% by weight of a substituted propane having the general formula:

wherein R is a member selected from the group consisting of methyl and ethyl and n and n are integers between 2 and 6 inclusive, and wherein m and m are integers between 1-6 inclusive.

2. A molding composition comprising a ureaformaldehyde resin and between about 2% and 15% by weight of a substituted propane wherein said alkylene group contains between 2 and 6 carbon atoms having the general formula:

wherein R, is a member selected from the group consisting of methyl and ethyl and n and n are integers between 2 and 6 inclusive, and wherein m and m are integers between 1-6 inclusive.

3. A molding composition comprising a ureaformaldehyde resin and between about 2% and 15% by weight of 2-hydroxy, l-hydroxyalkyleneoxy, B-methoxyethoxy-propane wherein said alkylene group contains between 2 and 6 carbon atoms.

4. A molding composition comprising a ureaformaldehyde resin and between about 2% and 15% by weight of 2-hydroxy, l-hydroxalkyleneoxy, 3-ethoxyethoxy-propane wherein said alkylene group contains between 2 and 6 carbon atoms.

5. A molding composition comprising a ureaformaldehyde resin and between about 2% and 15% by weight of 2-hydroxy, l-hydroxyalkyleneoxy, 3-ethoxyethoxyethoxy-propane wherein said alkylene group contains between 2 and 6 carbon atoms.

6. A molding composition comprising a ureaformaldehyde resin and between about 2% and 15% by weight of 2-hydroxy, l-hydroxyethoxy, 3-methoxyethoxy-propane.

7. A molding composition comprising a ureaformaldehyde resin and between about 2% and 15% by weight of 2hydroxy, l-hydroxethoxyethoxy, 3-ethoxyethoxy-propane.

8. A molding composition comprising a ureaformaldehyde resin and between about 2% and 15% by weight of 2-hydroxy, l-hydroxyethoxyethoxy, 3-ethoxyethoxyethoxy-propane.

- No references cited. 

1. A MOLDING COMPOSITION COMPRISING AN AMINOPLAST RESIN SELECTED FROM THE GROUP CONSISTING OF A MELAMINE-FORMALDEHYDE RESIN AND A UREAFORMALDEHYDE RESIN AND BETWEEN ABOUT 2% AND 15% BY WEIGHT OF A SUBSTITUTED PROPANE HAVING THE GENERAL FORMULA: 